JP6220822B2 - Metal lithium electrode plate - Google Patents

Description

  The present invention relates to an electrode plate, and more particularly to a metal lithium electrode plate having a gate layer.

Compared with existing non-lithium system battery systems, lithium-based battery systems have higher work voltage (3.6V), higher energy density (120Wh / kg), lighter weight, longer lifespan, and better environmental protection There are advantages such as.
Among battery systems that use lithium as an active material, the lithium battery system that is developed the fastest is a rechargeable metal lithium battery, which has a very high energy density, but is highly metal lithium, It reacts easily with the electrolyte, and the metal lithium battery becomes unstable, which causes a safety problem. Based on safety considerations, the development of rechargeable lithium batteries will shift from rechargeable metal lithium batteries to two systems: rechargeable lithium alloy batteries and rechargeable lithium ion batteries.
Liquid rechargeable lithium-ion batteries use an electrolyte containing an organic solvent, so they are prone to volatilization and combustion, and do not become a perfect seal when the battery is packaged. There is a possibility of leakage, and there is a considerable risk of safety. In recent years, the safety of the lithium battery has been mainly studied, and a new rechargeable lithium polymer battery has been researched again. This greatly improves the safety with which a lithium battery is used by using a polymer electrolyte as the electrolyte in the battery instead of the original organic solvent.

However, in recent years, a large number of portable smart electronic products have emerged, and the performance of products continues to improve in order to demand newness and change for each generation of products. For this reason, in addition to the high demands for safety in the past, the battery system has a long operating time for electronic products. Therefore, the service life of the battery system has become an important issue for battery system research. The direction of research is shifting from the safety to extending the life of battery systems.
In the history of lithium battery system development, research on metal lithium battery systems was once suspended for safety reasons, but metal lithium is used directly as the active material of metal lithium battery systems, so other lithium ion battery systems Or, it is true that the energy density provided by metallic lithium battery systems is greater than these lithium compound battery systems compared to lithium polymer battery systems.
On the other hand, metallic lithium is a very active metal, and it is also true that violent oxidation-reduction reactions are likely to occur in metallic lithium itself unless it is in an appropriate storage environment or good operating environment. Therefore, in practical use, if the safety problem of metallic lithium battery can be effectively overcome and the difficulty in process or storage can be reduced, it can meet the demands of modern portable smart electronic products.

  The present invention effectively overcomes the disadvantages of the prior art described above by providing an electrode plate made of metallic lithium.

  An object of the present invention is to provide a metal that can be produced directly like an electrode plate structure made of a general lithium compound by sealing a metal lithium layer with at least one of a current collecting layer and a gate layer. A lithium electrode plate is provided. Therefore, a battery system having an energy density higher than that of a general lithium compound can be manufactured only by using an existing process technology.

  Another object of the present invention is to gradually change the original structure of the gate layer into the form of a fine lithium alloy material by causing the gate layer to alloy with the lithium ions and / or the metal lithium layer by the action of the medium. It is intended to provide a metal lithium electrode plate that expands the entire volume (a large number of holes are generated due to loose stacking), while a lithium ion has an electrochemical reaction with the metal lithium layer.

  Still another object of the present invention is to provide a metal lithium electrode plate in which a general positive electrode plate is directly mounted on a metal lithium electrode plate to form a power supply unit having metal lithium.

In order to achieve the above object, the present invention includes a metallic lithium layer, a plurality of gate layers, and a current collecting layer. The current collecting layer has a plurality of holes, and each hole has at least one opening. The plurality of gate layers are provided corresponding to the plurality of holes, and the metal lithium layer is provided corresponding to the plurality of gate layers.
In the metal lithium electrode plate disclosed in the present invention, the gate layer causes an alloying reaction with lithium ions and / or the metal lithium layer by the action of the medium, so that the original structure of the gate layer is gradually formed into a form of a particulate lithium alloy material. And the entire volume is expanded (a large amount of holes are generated because the stacking is loose), while the lithium ion becomes a pathway for causing an electrochemical reaction with the metal lithium layer. The metal lithium electrode plate disclosed in the present invention is directly mounted on a general positive electrode plate, thereby forming a power supply unit having a high energy density.

  Hereinafter, in order to further understand the object, technical contents, features, and effects that can be achieved, the present invention will be described in detail with reference to specific examples.

It is a structure schematic diagram of embodiment of the metal lithium electrode plate which concerns on this invention. It is a structure schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention. It is a structure schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention. It is a structure schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention. FIG. 1B is a structural schematic diagram after the gate layer of FIG. 1A is alloyed. FIG. 1B is a structural schematic diagram after the gate layer of FIG. 1B is alloyed. FIG. 1D is a structural schematic diagram after the gate layer of FIG. 1C is alloyed. 1D is a structural schematic diagram after the gate layer of FIG. 1D is alloyed. FIG. It is a structure schematic diagram of embodiment of the metal lithium electrode plate which concerns on this invention. It is a structure schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention. It is a structure schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention. It is a structural schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention, Among these, the form of the other ion conduction layer is disclosed. FIG. 3B is a structural schematic diagram after the gate layer of FIG. 3A is alloyed. FIG. 3B is a structural schematic diagram after the gate layer of FIG. 3B is alloyed. FIG. 3C is a structural schematic diagram after the gate layer of FIG. 3C is alloyed. It is a structure schematic diagram after the gate layer of FIG. 3D is alloyed. It is a structure schematic diagram of embodiment of the metal lithium electrode plate which concerns on this invention. It is a structure schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention. It is a structure schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention. It is a structural schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention, Among these, the form of an ion conduction layer is disclosed. FIG. 5B is a structural schematic diagram after the gate layer of FIG. 5A is alloyed. FIG. 5B is a structural schematic diagram after the gate layer of FIG. 5B is alloyed. FIG. 5C is a structural schematic diagram after the gate layer of FIG. 5C is alloyed. It is a structure schematic diagram after the gate layer of FIG. 5D is alloyed. It is a structural schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention, Among these, the form of an ion conduction layer is disclosed. It is a structural schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention, Among these, the form of the other ion conduction layer is disclosed. It is a structural schematic diagram of other embodiment of the metal lithium electrode plate which concerns on this invention, Among these, the form of another ion conduction layer is disclosed. FIG. 7B is a structural schematic diagram after an alloying reaction is performed on the gate layer in FIG. 7A. FIG. 8 is a structural schematic diagram after an alloying reaction is performed on the gate layer in FIG. 7B. FIG. 7B is a structural schematic diagram after an alloying reaction is performed on the gate layer in FIG. 7C. It is a structure schematic diagram of an embodiment of a battery core according to the present invention. It is a structure schematic diagram of the package form of the metal lithium electrode plate which concerns on this invention.

The gist of the present invention is that a lithium metal electrode plate formed in a power supply unit in which a lithium metal electrode plate is directly stored and operated in a normal environment and has a higher energy density and safety than a general positive electrode plate Is to provide.
The metal lithium electrode plate includes a metal lithium layer, a plurality of gate layers, and a current collecting layer, wherein the current collecting layer has a plurality of holes, each hole having at least one opening, The gate layer is installed in correspondence with the plurality of holes, the metal lithium layer is installed in correspondence with the plurality of gate layers, and the metal lithium layer is installed adjacent to the gate layer or separated from the gate layer. However, in the case where they are installed adjacent to each other, the metal lithium layer and the gate layer may or may not contact each other. By adding the medium, the alloying reaction of the gate layer proceeds to cause the redox reaction of the metal lithium layer. Furthermore, it becomes easy to combine with a general electrode plate to form a power supply unit having a high energy density.

  Hereinafter, the gist of the present invention will be described in more detail. The following is a description of several different embodiments, which are merely examples, and do not limit the scope of the claims of the present invention.

  First, simultaneously refer to FIG. 1A and FIG. 2A. FIG. 1A is a structural schematic diagram of an embodiment of a metal lithium electrode plate according to the present invention, and FIG. 2A is a form after the gate layer in FIG. 1A is alloyed.

  In the drawing, a local cross section of the metallic lithium electrode plate 10A of the present invention is shown. The bottom is the metal lithium layer 12, the current collecting layer 14 having a plurality of holes H is above the bottom, and the gate layer 142 has an opening H of the hole H at one end away from the metal lithium layer 12. And covering the surface of the current collecting layer 14 locally. In this embodiment, the gate layer 142 and the metal lithium layer 12 are not actually in contact.

Structurally, when the metal lithium electrode plate 10A is applied to a power supply unit (not shown), the metal lithium electrode plate 10A serves as a negative electrode plate, and an electrochemical reaction occurs in an electrochemical system inside the power supply unit. Since the gate layer 142 and lithium ions and / or metal lithium do not interact with each other before being performed, the structure of the gate layer 142 is stable and good. Accordingly, when the current collecting layer 14 and / or the gate layer 142 is provided, the metallic lithium layer 12 is well protected and does not directly contact the medium, and the manufacturing process is performed under conditions of higher temperature and higher pressure. The metal lithium layer 12 can be operated.
However, when the electrochemical reaction in the power supply unit begins to proceed, that is, when there is a voltage difference between the positive and negative electrodes of the power supply unit (for example, charging is performed), lithium ions provided from the medium Lithium ions released from the positive electrode plate migrate from the positive electrode plate to the metal lithium electrode plate 10A, and after reaching the metal lithium electrode plate 10A, a material capable of reacting with lithium ions and / or metal lithium in the gate layer 142 First, an alloying reaction occurs. As a result, the initial lattice structure of the gate layer 142 gradually collapses to become an alloy material having a loose lattice structure. When the alloy material comprising the gate layer 142 and lithium ions reaches a predetermined amount, the alloy material becomes a medium (electrolyte solution). ) Is filled from the opening O into the hole H. Finally, the medium is guided to the hole H by the gap in the alloy material to form an ion channel of lithium ions, and in contact with the metal lithium layer 12, the current collecting layer 14 and the gate layer 142 in the metal lithium electrode plate 10A. And the potential of the metallic lithium layer 12 both approach. Its structure is shown in FIG. 2A. Among these, the medium may be, for example, a liquid electrolyte, a solid electrolyte, a colloidal electrolyte, a liquid ion, or a combination of the above materials.

More specifically, when a voltage is not generated between the positive electrode and the negative electrode of the power supply unit, the chemical reaction in the power supply unit does not proceed because the power supply unit is not driven by electric power. Reaction does not occur with ions).
When the power supply unit performs charging, that is, when the power supply unit performs formation using the first charge as an example, the gate layer 142 is not in contact with the metal lithium layer 12, so that lithium ions in the gate layer 142 and The component that can react with metallic lithium only performs an alloying reaction with lithium ions provided from the medium. In short, almost all of the components that can react with lithium ions and / or metallic lithium in the gate layer 142 as the formed alloy material begins to occur at the interface where the gate layer 142 contacts the medium and the reaction time increases. Reacts with lithium ions. At this time, the gate layer 142 is almost completely collapsed to form an alloy material, and the alloy material gradually fills the holes H of the current collecting layer 14 as the amount increases. As a result, the medium reaches the surface of the metallic lithium layer 12 through the alloy material, and an exchange action between ions and electrons occurs. In other words, after the power supply unit is completely formed or charged several times, after the gate layer 142 for distinguishing the metal lithium layer 12 from the medium is first broken by an alloying reaction, the medium is broken. It is filled with the hole H by the alloy material) and comes into contact with the metal lithium layer 12. Thereby, the metal lithium layer 12 causes an electrochemical reaction in the power supply unit. From this, it can be seen that after the electrochemical reaction, the gate layer 142 is collapsed from the initial structure to the fine alloy material structure by the alloying reaction and cannot return to the initial structure.
From the viewpoint of functionality, the gate layer 142 can act on any substance by acting as a sealing structure mainly using the characteristics of its metal structure or metalloid structure before an electrochemical reaction occurs in the power supply unit. The metal lithium layer 12 is completely sealed so as not to occur. However, when an electrochemical reaction occurs, the gate layer 142 gradually collapses to become an alloy material. In other words, the metal structure of the gate layer 142 finally disappears and exists in the power supply unit in an alloy state.

  The other main function of the metal lithium layer 12 is to approximate the potential of the gate layer 142 to the potential of the metal lithium layer 12, that is, to maintain a state of approaching 0 volts. In short, the gate layer 142 is maintained at 0 volts at which metallic lithium is formed, so that the structure of the alloy material generated when lithium ions in the medium undergo an alloying reaction with the gate layer 142 becomes more delicate and uniform. .

In addition to the above embodiment, the gate layer 142 covers the opening O, and further fills the inside of the hole H as shown in FIG. 1B. 2B shows a structural schematic diagram after the gate layer 142 in FIG. 1B is alloyed, FIG. 1C shows a case where the gate layer 142 is completely filled with holes H, and FIG. 2C shows the case in FIG. The structural schematic diagram after the gate layer 142 is alloyed is shown.
Although an example in which the gate layer 142 is not in contact with the metal lithium layer 12 will be described in these embodiments, a structure in which the gate layer 142 is in contact with the metal lithium layer 12 may actually be used. Here, although the hole H of the current collecting layer 14 is shown in the form of a through hole, the hole H may be a blind hole as shown in FIG. 1D.
FIG. 2D shows a structural schematic diagram after the gate layer 142 in FIG. 1D is alloyed. In addition, the metal lithium layer 12 in these embodiments completely covers the surface of one side of the current collecting layer 14, but may be a form that locally covers the surface of the current collecting layer 14. For example, when the opening O of the current collecting layer 14 becomes an opening of a through hole, the metallic lithium layer 12 is filled up to the other end of the opening O so as to cover the opening O corresponding to the gate layer 142, or It only fills to the other end. That is, the metallic lithium layer 12 may cover the current collecting layer 14 locally or completely.

As shown in FIG. 1D and FIG. 2D, the lithium ion is not precipitated on the outer surface before entering the current collecting layer 14, and the outer surface where the current collecting layer 14 is exposed is plated in an overcharged state. In order to avoid the occurrence of lithium protrusions due to the progress of the reaction, the current collecting layer 14 is provided with several insulating areas A on the outer surface on one side not adjacent to the metal lithium layer 12. The insulating area A does not have conductivity, and the structural form thereof may be an electrically insulating layer shown in this embodiment, or may be an electrically insulating surface that has been surface-treated. For example, a surface treatment is performed on the outer surface where the current collecting layer 14 is exposed to inactivate its conductive properties.

The material of the current collecting layer is selected from materials that do not cause an alloying reaction with copper, nickel, iron, zinc, gold, silver, titanium, or lithium.
The gate layer 142 may include one or many kinds of metals, includes a metal material and / or a metalloid material, and a material that cannot be formed into a lithium alloy other than a material that can be formed into lithium and a lithium alloy in various materials of the gate layer 142. May be included. These two types of materials may exist in any form of non-alloy or alloy. For example, the non-alloyed state is formed by patterned sputtering, vapor deposition, or plating. However, in the composition of the gate layer 142, the content of the material that can be formed in the lithium alloy is 0.1% by weight or more, and the balance is lithium. And a material capable of generating an alloying reaction. Among these, examples of the material that can be formed on the lithium alloy include aluminum, tin, silicon, aluminum alloy, tin alloy, silicon alloy, and other single metal or alloy materials. For example, copper, nickel, iron, titanium, zinc, silver, gold, or a combination thereof may be used.
The material that can be formed into the lithium alloy may be aluminum, tin, silicon, aluminum alloy, tin alloy, silicon alloy, other single metal or alloy material, or various metals or alloy materials, formed into lithium alloy The material that cannot be used may be a single material or a combination of a plurality of materials, such as copper, nickel, iron, titanium, zinc, silver, gold, or a combination thereof. For example, when the gate layer 142 is dialloy, it may be a nickel metal that can be formed into an alloy with lithium ions / lithium metal and a nickel-tin alloy that includes nickel metal that does not cause an alloying reaction with lithium. The tin content is 0.1% by weight or more.

  1A to 1D and FIGS. 2A to 2D show that the lithium metal layer and the gate layer are disposed apart from each other. In the following FIGS. 3A to 3D, FIGS. 4A to 4D, FIGS. 5A to 5D, and FIGS. 6A to 6D, forms in which the metal lithium layer and the gate layer are installed adjacent to each other are disclosed.

Reference is made to FIGS. 3A to 3D disclose a mode in which a metal lithium layer and a gate layer are installed adjacent to each other.
The metal lithium electrode plate 10B includes a metal lithium layer 12, a plurality of gate layers 142, and a current collecting layer 14 having a plurality of holes H, and is adjacent to one end of the metal lithium layer 12, as shown in FIG. 3A. The gate layer 142 covers the opening O of the hole H. FIG. 3B discloses a form in which the gate layer 142 covers the opening O and fills the hole H. The opening O is adjacent to the metal lithium layer 12.
Still referring to FIG. The gate layer 142 fills the hole H, but does not cover the surface of the current collecting layer 14, and the gate layer 142 is adjacent to the metal lithium layer 12. The metallic lithium layer 12 in FIGS. 3A-3C covers the electrical layer 14 locally or completely. In addition, the ion conductive layer 16 is also applied to this embodiment, and FIG. 3D is a structural schematic diagram including a kind of ion conductive layer 16. Each of FIGS. 4A to 4D corresponding to FIGS. 3A to 3D is a form in which an alloy material is formed by alloying the gate layer 142. Among these, the structural features and material properties relating to the metal lithium layer 12, the current collecting layer 14, the gate layer 142, the ion conductive layer 16 and the insulating area (not shown) have already been described in the previous paragraph, and are omitted here.

The above embodiments disclose various structural correspondence relationships in which the gate layer is in the hole of the current collecting layer and the opening thereof, and the positional relationship between the different metal lithium layers and the gate layer according to the corresponding positional relationships in which the metal lithium layer and the gate layer are different from each other. There are various forms of gate layers with different positional relationships.
In the following FIG. 5A to FIG. 5C, as an example in which the gate layer completely fills the hole and is adjacent to the metal lithium layer, the structure of the hole of the metal lithium layer and the collector layer and the structure of the opening The correspondence relationship will be described. Of course, these forms may be combined with other forms of gate layers, or may be combined with other metal lithium layers and gate layers having different installation relationships, and the ion conductive layer and insulating area are merged. May be.

5A, a metal lithium electrode plate 10C including a metal lithium layer 12, a plurality of gate layers 142 and a current collecting layer 14 having a plurality of holes H is disclosed. Among these, the gate layer 142 is filled in the hole H, the metal lithium layer 12 is disposed adjacent to the gate layer 142 so as to cover the opening O of the hole H, and the metal lithium layer 12 in FIG. In addition, the hole H is filled and adjacent to the gate layer 142 filled in the hole H.
In FIG. 5C, the metal lithium layer 12 fills the hole H and is adjacent to the gate layer 142 in the hole H. Among these, the above embodiments have been described in the form where the metal lithium layer 12 and the gate layer 142 are not in contact. However, when the metal lithium layer 12 and the gate layer 142 are adjacent to each other, they may be in contact with each other. .
FIG. 5D is a structural schematic diagram including a kind of ion conductive layer 16. 6A to 6D are schematic diagrams correspondingly showing the structure after the gate layer 142 in FIGS. 5A to 5D is alloyed.

  The ion conductive layer will be described in more detail. Please refer to FIG. 7A and FIG. 8A. 7A is a structural schematic diagram of another embodiment of the metal lithium electrode plate according to the present invention, and FIG. 8A is a form after the gate layer in FIG. 7A is alloyed.

The metal lithium electrode plate 10 </ b> A in this form includes the metal lithium layer 12, the current collecting layer 14, and the gate layer 142, and further includes the ion conductive layer 16. The ion conductive layer 16 is provided between the metal lithium layer 12 and the current collecting layer 14 and the gate layer 142. In actual use, the ion conductive layer 16 is composed of the metal lithium layer 12, the current collecting layer 14 and the gate layer 142. They may be in contact with each other at the same time, or substantially only in contact with the metal lithium layer 12 and the current collecting layer 14. The structure of the ion conductive layer may be a porous layer structure, a net structure, a columnar structure, or a combination of the above structures.
The form disclosed in FIG. 7A describes an example in which the metal lithium layer 12 and the current collecting layer 14 are substantially in contact with each other, and the structure of the metal lithium electrode plate 10A in this form is as follows. The layer 12 includes an ion conductive layer 16, a gate layer 142 located at the end of the opening O, and a current collecting layer 14 having the opening O. Among these, the characteristics of the metal lithium layer 12, the current collecting layer 14, and the gate layer 142 are described in the above paragraphs, so only the characteristics of the ion conductive layer 16 will be described in detail here.

First, the main function of the ion conductive layer 16 is to assist ions to be conducted between the current collecting layer 14, the gate layer 142, and the metal lithium layer 12. Its presence does not reduce the conductivity between the current collecting layer 14 and the metal lithium layer 12, and is therefore most preferable for the ion conductive layer 16 disposed between the metal lithium layer 12, the current collecting layer 14, and the gate layer 142. The form has ionic conductivity and conductivity at the same time. Among these, the ion conductivity is formed from the material of the ion conductivity 16 itself, the gap and the electrolyte material (the electrolyte material is a liquid electrolyte, a colloidal electrolyte, a solid electrolyte, or a liquid electrolyte) or a combination thereof. However, the conductivity of the ion conductive layer is not necessarily obtained from the ion conductive layer 16 itself, but the volume is increased after the gate layer 142 is alloyed, and the expanded alloyed material is used as the conductive material, and the alloyed material is the ion conductive layer. The current collecting layer 14 and the metal lithium layer 12 are electrically connected through the 16 gaps.
Regarding the chemical characteristics, since the ion conductive layer 16 is in direct contact with the metallic lithium layer 12, no alloying reaction occurs with the metallic lithium layer 12 in any state. A depletion area 162 exists between the ion conductive layer 16 shown in FIG. 7A and the gate layer 142 at the other end of the opening O. The depletion area 162 is a gap that is not filled with a substance before the electrochemical reaction proceeds in the power supply unit, and may be a gap that includes only an electrolyte (among these, the electrolyte material is a liquid electrolyte, a colloid) It may be an electrolyte, a solid electrolyte, or a liquid ion). However, as described above, when the electrochemical reaction in the power supply unit starts to proceed, the alloy material composed of the gate layer 142 and lithium ions gradually fills the depletion area 162 in the opening O and further into the ion conductive layer 16. fill in. That is, after the electrochemical reaction proceeds and the alloy material is filled in the depletion area 162 and the ion conductive layer 16, ions and electrons are converted into the metal lithium layer 12, the current collecting layer 14, and the gate layer 142 by the alloy material and the electrolyte. The structure is shown in FIG. 8A.
From this, the conductivity of the ion conductive layer 16 is not realized by its own material properties, but the ion conductive layer 16 is filled with an alloy substance after the gate layer 142 is alloyed. Can be realized. Among these, the ion conductive layer 16 of this form is generally a ceramic insulating material, a polymer material, a liquid electrolyte, a colloidal electrolyte, a solid electrolyte, or a liquid ion other than a conductive material or the above material and the ion conductive layer 16 itself. Various combinations of gaps may be included. Among these, examples of the conductive material include metal materials, alloy materials, and conductive carbon materials (for example, carbon black, hard carbon, carbon nanotube, graphite, graphene, and the like). The combination of the above-mentioned various materials and the gap between the ion conductive layer 16 itself includes that a metal or alloy film is formed by plating, vapor deposition, or sputtering on the original conductive material, and the ceramic insulating material is a metal oxide Metal sulfides, metal nitrides, or acid-reacted metal materials (eg, phosphorylated metal).
In general, since there are a large number of gaps in the ion conductive layer, the ion conductive layers become paths of ion conduction, and these paths pass through the ion conductive layer by collecting the alloyed gate layer 142 whose volume is expanded. By connecting the layer 14 and the metallic lithium layer 12, the effect of conducting electrons is reached.

  In addition to the above configuration, as shown in FIG. 7B, a part of the ion conductive layer 16 in the metal lithium electrode plate 10A is filled in the other end of the opening O of the current collecting layer 14 and corresponds to the gate layer 142. And substantially in contact with either the metal lithium layer 12 or the gate layer 142. After the electrochemical reaction starts in the power supply unit, the alloy material composed of the gate layer 142 and lithium ions is gradually filled into the ion conductive layer 16, whereby the alloy composed of the gate layer 142, as shown in FIG. 8B. A material contacts the metallic lithium layer 12 to provide electrical conductivity.

In the embodiment disclosed in FIG. 7C, the structure of the ion conductive layer 16 in the metal lithium electrode plate 10A is columnar, and the ion conductive layer 16 in this form locally covers the current collecting layer 14 and the metal lithium layer 12, The opening O (opening area) of the current collecting layer 14 is intentionally avoided, and is formed only between the current collecting layer 14 and the metal lithium layer 12 in the non-opening area. The material of the ion conductive layer 16 in this form is special in comparison with a general form, and is usually only a conductive material, such as a metal material, an alloy material or various conductive carbon materials, or a conductive material, a polymer material, and the like. This is a combination of gaps in the ion conductive layer 16 itself. Here, electroconductivity is strengthened by performing plating, vapor deposition, and sputtering on the original conductor material to form a metal or alloy film.
Since the columnar ion conductive layer 16 has a large amount of gaps, it can be provided as a channel that conducts ions, and both ends of the ion conductive layer 16 are in direct contact with the metal lithium layer 12 and the current collecting layer 14. Conducting effect can be achieved. Of course, once the electrochemical reaction has started in the power supply unit, the alloy material composed of the lithium ions and the gate layer 142 is gradually filled into the gap between the columnar ion conductive layers 16 as shown in FIG. The resulting alloy material is brought into contact with the metallic lithium layer 12.

Among these, the conductivity of the ion conductive layer 16 is the conductive material of the ion conductive layer 16 itself, such as a metal material, an alloy material, a conductive carbon material (for example, carbon black, hard carbon, carbon nanotube, graphite, graphene, etc.), etc. Or from an alloy material formed after the gate layer 142 is alloyed, or from a lithium protrusion generated between the current collecting layer 14 and the metal lithium layer 12, Or it can provide from all the said structures.
The reason why the ion conductive layer 16 takes the form of a lithium protrusion is the environment infiltrated with the electrolyte. When the potential of the metallic lithium electrode plate 10A is close to 0 volts, the potential of the current collecting layer 14 is the potential of the metallic lithium layer 12. Therefore, a depositing action is likely to occur at the interface of lithium ions. That is, in the process of electrochemical reaction, lithium current is easily deposited on the surface adjacent to the ion conductive layer 16 and the lithium metal protrudes. Things are formed.
Since the ion conductive layer 16 has a large amount of gaps, when the lithium protrusions grow from the current collecting layer 14 to the metal lithium layer 12, when the lithium protrusions contact the metal lithium layer 12 through the gaps of the ion conductive layer, Between the current collecting layer 14 and the metal lithium layer 12, an ion conductive layer 16 structure of a branch-like crystal (lithium protrusion) structure component that conducts the current collecting layer 14 and the metal lithium layer 12 (the structure is a structure of 7C) Is formed).
Compared with known power supply units, when lithium metal is deposited in a general power supply unit and lithium protrusions (dendritic crystals) are formed, the separation layer breaks through, causing an internal short circuit problem. While the lithium protrusion disclosed in the present invention may interfere with the function of the power supply unit, the current collection layer 14 is generated on the surface adjacent to the metal lithium layer 12, so that the generated lithium protrusion is inside the battery. Since the structure is not destroyed, there is no problem of an internal short circuit, and the resistance value inside the battery is lowered by increasing the surface area of the electrical connection between the current collecting layer 14 and the metal lithium layer 12 by forming a lithium protrusion. The

  FIG. 9A is a schematic structural diagram of one embodiment of a battery core according to the present invention. Among these, the metal lithium electrode plate (10A) disclosed in FIG. 7A will be described as an example.

The battery core BC in the present embodiment includes two first electrode plate units 20 and a second electrode plate unit 10A. Among these, each of the first electrode plate units 20 includes an active material layer 22, a first current collection layer 24, and a separation layer 26, and the first current collection layer 24 is one of the active material layers 22. The separation layer 26 is provided on the other side of the active material layer 22. That is, the active material layer 22 is sandwiched between the first current collecting layer 24 and the separation layer 26, and the second electrode plate unit 10 </ b> A is sandwiched between the two first electrode plate units 20.
In addition, the second electrode plate unit 10A includes a second current collecting layer 14 having a hole H, a gate layer 142 at an end of the hole H, an ion conductive layer 16, a metal lithium layer 12, and an ion conductivity. The second current collecting layer 14 including the layer 16, the second current collecting layer 14 having the hole H, and the gate layer 142 at the end of the hole H, on the upper and lower sides of the second electrode plate unit 10 </ b> A. Are disposed adjacent to the separation layer 26 of the first electrode plate unit 20.

FIG. 9B is a structural schematic diagram of a form in which the metal lithium electrode plate according to the present invention is packaged. Since the second electrode plate unit 10A can be exposed to a normal environment, the peripheral edge of the second electrode plate unit 10A is further provided. The package unit 30 is installed.
In the example of the present embodiment, the package unit 30 is made of a material capable of barriering water and gas, and the form may be a frame shape or another shape. For example, the package unit 30 may be a single layer silica gel frame or a multilayer silica gel frame. Here, a three-layer silica gel frame will be described as an example, but this is an example and does not limit the scope of the present invention.
The package unit 30 is not a necessary structure of the second electrode plate unit 10A. For example, when the second electrode plate unit 10A does not include an independent package unit, the package unit 30 is mounted on the first electrode plate unit 20, Packaging may be performed.

More specifically, after the medium is adsorbed to the separation layer 26 of the first electrode plate unit 20 (for example, an electrolytic solution (not shown)), the first electrode plate unit is subjected to an appropriate process (for example, hot pressing). 20 and the second electrode plate unit 10A are adhered to each other. As a result, the combination of the battery cores BC is completed. Therefore, when the battery core BC is charged, the medium flows from the first electrode plate unit 20 toward the second electrode plate unit 10A and a large amount of lithium ions are discharged. Carry to the second electrode plate unit 10A.
A large amount of lithium ions in the medium is gated by entering through the opening O of the second current collecting layer 14 in the second electrode plate unit 10A, contacting the gate layer 142, and causing the gate layer 142 to proceed with an alloying reaction. An alloying reaction with the layer 142 is performed to form an alloy having lithium. Thereby, the potentials of the second current collecting layer 14, the gate layer 142, and the ion conductive layer 16 in the second electrode plate unit 10A approach the potential of the metal lithium layer 12, that is, the entire second electrode plate unit 10A. Is relatively close to 0 volts.

  Furthermore, after lithium ions in the medium are repeatedly charged and discharged several times, that is, after several times of alloying reaction and dealloying reaction, consumption is inevitable. For example, a part of lithium ions is reduced. The incapable gate layer is released to the medium as a lithium alloy, or some of the lithium ions are consumed as lithium protrusions. At this time, the alloy material filled in the hole H is used as a bridge of the metal lithium layer 12, and the lithium ions of the metal lithium layer 12 are led back to the chemical system inside the battery core, so that sufficient lithium ions can be returned to the battery core. It can be provided to BC to extend the life of the entire battery core.

  The above are only preferred embodiments of the present invention and do not limit the scope of the present invention. Any changes or modifications equivalent to the features and spirit of the claims according to the present invention should be included in the claims of the present invention.

10A Metal Lithium Electrode Plate / Second Electrode Plate Unit 10B Metal Lithium Electrode Plate 10C Metal Lithium Electrode Plate 12 Metal Lithium Layer 14 Current Collection Layer / Second Current Collection Layer 142 Gate Layer 16 Ion Conductive Layer 162 Depletion Area 20 First Electrode plate unit 22 active material layer 24 first current collecting layer 26 separation layer 30 package unit A insulation area BC battery core H hole O opening

Claims (22)

And a current collector layer, and a metallic lithium layer, a plurality of gate layers, viewed contains at least one insulating area, stored in a normal environment prior to application to the battery system, a lithium metal electrode plate is operable,
The current collecting layer has a plurality of holes, and each of the holes has at least one opening;
The metallic lithium layer is disposed under the current collecting layer or in the hole, and a part of the metallic lithium layer is exposed through the opening,
The plurality of gate layers cover the opening and shield the exposed side of the metallic lithium layer not covered by the current collecting layer;
The at least one insulating area is located on an outer surface of one side of the current collecting layer not adjacent to the metal lithium layer;
The gate layer comprises at least one material capable of being alloyed with lithium ions or metallic lithium;
The gate layer can change into a fine alloy material after the alloying reaction, and becomes a path for causing an electrochemical reaction ,
Metal lithium electrode plate.   The metal lithium electrode plate according to claim 1, wherein the gate layer further covers the opening.   The metal lithium electrode plate according to claim 1, wherein the gate layer further covers the opening and fills the hole.   The metal lithium electrode plate according to claim 1, wherein the gate layer is further filled in the hole.   The metal lithium electrode plate according to claim 1, wherein the gate layer locally covers the current collecting layer.   The metal lithium electrode plate according to claim 1, wherein the opening is a through hole and / or a stop hole.   The metal lithium electrode plate according to claim 6, wherein the metal lithium layer further covers the opening. A metal lithium electrode plate including a current collecting layer, a metal lithium layer, and a plurality of gate layers,
The current collecting layer has a plurality of holes, and each of the holes has at least one opening;
The metallic lithium layer is disposed under the current collecting layer or in the hole, and a part of the metallic lithium layer is exposed through the opening,
The plurality of gate layers cover the opening and shield the exposed side of the metallic lithium layer not covered by the current collecting layer;
The gate layer comprises at least one material capable of being alloyed with lithium ions or metallic lithium;
The opening is a through hole and / or a stop hole,
The metal lithium layer further covers the opening and fills the hole;
The gate layer may change to a fine alloy material after alloying reaction,
Metal lithium electrode plate. A metal lithium electrode plate including a current collecting layer, a metal lithium layer, and a plurality of gate layers,
The current collecting layer has a plurality of holes, and each of the holes has at least one opening;
The metallic lithium layer is disposed under the current collecting layer or in the hole, and a part of the metallic lithium layer is exposed through the opening,
The plurality of gate layers cover the opening and shield the exposed side of the metallic lithium layer not covered by the current collecting layer;
The gate layer comprises at least one material capable of being alloyed with lithium ions or metallic lithium;
The opening is a through hole and / or a stop hole,
The metal lithium layer is characterized in that it is further filled in the hole, metallic lithium electrode plates. The metal lithium electrode plate according to claim 8 or 9 , wherein the metal lithium layer further completely covers the opening.   2. The metal lithium electrode plate according to claim 1, wherein the metal lithium layer is disposed adjacent to the plurality of gate layers, and the gate layer and the metal lithium layer are in contact or not in contact with each other. A metal lithium electrode plate including a current collecting layer, a metal lithium layer, and a plurality of gate layers,
The current collecting layer has a plurality of holes, and each of the holes has at least one opening;
The metallic lithium layer is disposed under the current collecting layer or in the hole, and a part of the metallic lithium layer is exposed through the opening,
The plurality of gate layers cover the opening and shield the exposed side of the metallic lithium layer not covered by the current collecting layer;
The gate layer comprises at least one material capable of being alloyed with lithium ions or metallic lithium;
The metal lithium layer is disposed apart from the plurality of gate layers ;
The gate layer may change to a fine alloy material after alloying reaction,
Metallic lithium electrode plate. A metal lithium electrode plate including a current collecting layer, a metal lithium layer, a plurality of gate layers, and an ion conductive layer ,
The current collecting layer has a plurality of holes, and each of the holes has at least one opening;
The metallic lithium layer is disposed under the current collecting layer or in the hole, and a part of the metallic lithium layer is exposed through the opening,
The plurality of gate layers cover the opening and shield the exposed side of the metallic lithium layer not covered by the current collecting layer;
The ion conductive layer is disposed adjacent to the metal lithium layer;
The ion conductive layer does not generate an alloying reaction with the metal lithium layer,
The gate layer comprises at least one material capable of being alloyed with lithium ions or metallic lithium;
The gate layer may change to a fine alloy material after alloying reaction,
Metallic lithium electrode plate.   14. The metal lithium electrode plate according to claim 13, wherein the ion conductive layer is at least locally in contact with the current collecting layer and / or the metal lithium layer and / or the gate layer.   The metal lithium electrode plate according to claim 13, wherein the ion conductive layer further has conductivity.   14. The metal lithium electrode plate according to claim 13, wherein the structure type of the ion conductive layer is a porous layer structure, a net structure, a columnar structure, or a combination of the above structures.   The metal lithium electrode plate according to claim 13, wherein the ion conductive layer further includes a ceramic insulating material, a polymer material, a liquid electrolyte, a colloidal electrolyte, a conductive material, or a combination of the above materials.   2. The metal lithium electrode plate according to claim 1, wherein a material of the current collecting layer is selected from materials that cannot be formed into an alloy with copper, nickel, iron, zinc, gold, silver, titanium, or lithium.   The gate layer includes at least one metal material and / or metalloid material, and includes a material that can be formed into a lithium alloy, and the material that can be formed into the lithium alloy causes an alloying reaction with lithium ions provided from the medium; The metal lithium electrode plate according to claim 1, wherein a material that can be formed on the lithium alloy is selected from aluminum, tin, silicon, lithium alloy, tin alloy, silicon alloy, or a combination thereof.   The metal lithium electrode plate according to claim 19, wherein the medium is selected from a liquid electrolyte, a solid electrolyte, a colloidal electrolyte, a liquid ion, or a combination of the above materials.   The material that can be formed into an alloy with lithium in the gate layer may be alloyed or non-alloyed, and the content of the material that can be formed into alloy with lithium is 0.1 wt% or more. Metal lithium electrode plate. The current pre-Symbol insulating area of conductive layer is electrically insulating layer, or a metal lithium electrode plate according to claim 1 is surface treated electrically insulating surface.

Images